Hydrogenated indane-diones and a method of producing the same



Patented Feb. 4, 1941 TUNITED STATES PATENT OFFICE HYDROGENATED INDANE-DIONES AND A METHOD orrnonnomo THE SAME Elisabeth Dane, Munich, Germany, assignor to Schering Corporation, Bloomfield, N. J., a corporation of New Jersey No Drawing. Application May 10-, 1938, Serial No. 207,061. In Germany May 10, 1937 14 Claims. (Cl. 260-397) This invention relates to new compounds of compounds containing conjugated double bonds the indane-dione series and more particularly may be used as the other reaction component. to hydrogenated indane-diones and a method Thus, all those compounds are suitable that have of making the same. already been subjected to the above mentioned Hydrogenated indane-diones have not yet bee dien synthesis such as substituted butadienes, 5 described in the art. It has been found that for instance, isoprene, cyclopenta-dienes, cycloaccording to the present invention their manuhexa-dienes, phellandrene, myrcene and the like. facture is possible in an entirely new way by Products that are of special interest are obmaking use of the reaction of Diels and Alder. tained, for instance, by combining methyl-cy- For this purpose cyclopentene diones are caused clo pentene dione with l-vinyl-3A-dihydrom to react with compounds containing so -called naphthalenes, for instance, with 1-viny1-3,4-diconjugated double bonds. The combination of hydro-6-methoXy-naphthalene whereby indanecyclopentene diones with'such compounds condione derivatives are obtained that are derived taining conjugated double bonds is carried out from the cyclopentano phenanthrene ring sys- 15 in a manner known to the chemist for carrying tem present in the well-known sex hormones. 15 out the above mentioned dien synthesis of Hence, by this method it is possible to produce Diels and Alder. (Compare, for instance, Gercompounds that have theproperties of sexual man Patents 526,168, 521,621, 545,398 and hormones.

544,523.) The following example serves to illustrate the It could not be foreseen that cyclopenteneinvention without, however, limiting the same 0 diones would react with compounds containing to it: conjugated double bonds, for hitherto it was not 3 grams of 1-methyl-cyclopentene-l-dioneknown that two carbonylic groups in neighbour- 4,5 areheated with 4 com. of dioxane and 3 com. ing position would make a double bond sufiiof butadiene in a closed container for 40 hours ciently capable of reacting with compounds conto 110-130. Thereafter dioxane and the excess 25 taining conjugated double bonds, i. c. it was of b-utadiene are distilled off in a vacuum and not known that these two carbonylic groups the residue is then distilled in a high vacuum of would render a double bond philodienic. about 0.1 mm. When the bath has reached a Hitherto it was only known that an aldehyde temperature of 120 a yellowish oil passes over J.

group in neighbouring position to a double bond that on cooling solidifies to crystals. The crys- 30 or two carbonylic groups at the ends of a double tals are twice recrystallised from ether. C01- bond were necessary to render the double bond orless cubes of the melting point 120 are obphilodienic. tained which represent tetrahydro-indane-dione. According to the present invention as reaction This compound shows with ferric chloride the components there may be used not only cycloreddish color reaction of enols. 35

pentene-1-dione2,3 but also other compounds In the same manner 1-vinyl-3,4-dihydro-6- of the cyclopentene dione series, for instance, methoxy-naphthalene yields with methyl-cycloits homologues such as l-methyl-cyclopentenepentene-dione a compound containing a partly 1-dione-4,5. Thus, for instance, with methylhydrogenated cyclopentano methyl phenan- 40 cyclopentene-1-dione-4,5 and butadiene the bithrene ring system, that by hydrogenation and 40 wow-(0,3,4)-8-:rnethyl-1,2dioxonon en-5 is obsaponification can be transformed into an oestained, that means a hydrogenated indane ditriol compound. Instead of the 6-methoxyone that is substituted at the carbon atom formnaphthalene derivative, of course, other substiing the bridge between the 5-membered ring tuted and unsubstituted vinyl-na-phthalenes may and the 6-membered ring. As the other reaction be used likewise yielding similar products. component containing two conjugated double Instead of using dioxane another solvent can bonds butadiene' may be used. Thus, butadiene be employed. Furthermore the reaction condiand cyclopentene-1-dione-2,3 yield according to tions, temperature, pressure, duration and' the this invention ,tetrahydro indane-dione or more like may be varied according to the nature of exactly bicyclo--(0,3,4) -1,2-dioxononen-5 in good the components used as well as to the end-prod- 50 yield. Hence, in contrast to the hitherto cusucts desired, provided that the principles of the tomary methods of building up the indane ring invention as set forth in the specification and in system in the present case the 6-membered ring the claims annexed hereto are observed. is attached to an already present 5-membered What I clai is;

ring. Instead of butadiene, of course, also other 1, A condensation product of a cyclopentene 55 IIIH 15 wherein X represents a member of the group consisting of hydrogen, a hydrocarbon radical, and a part of a cyclic hydrocarbon ring system common to both Xs, while Y represents a member of the class consisting of hydrogen and alkyl groups.

20 3. A hydrogenated indane-dione compound of the following formula;

25 v QD wherein X represents a member of the group consisting of hydrogen, a hydrocarbon radical, and a part of a cyclic hydrocarbon ring system common to both Xs.

4. A hydrogenated indane-dione compound of the following formula:

375? om /Ov Pa w A ll wherein Z represents a member of the class consisting of the hydroxyl group and groups capable of being converted with the'aid of hy drolysis into a hydroxyl group.

5. A condensationproduct of l-methyl-cyclopentene-1-dione-4,5 and a 1-vinyl-3,4-dihydronaphthalene.

6. A condensation product of 1-methy1-cyc1opentene-1-dione-4,5 and a 1-vinyl-3,-4-dihydrofi-hydroiqgnaphthalene wherein the G-hydroxy group may .be replaced by a, group capable of conversion into a hydroxy group.

7. A method of making a hydrogenated indanedione compound comprising reacting a cyclopentene-dione with a compound containing con- .jugated double bonds.

8. A method of making a hydrogenated indane- "dione compound comprising reacting a cyclopentene-dione with a compound containing contjugated double bond according to the dien synthesis of Diels and Alder.

9. Atmet-hod according to claim 8 wherein the reaction is carried out in the presence of a solvent.

10. A method according to claim 8.wherein the. reaction is carried out by heating the reaction mixture under pressure.

11. A method according to claim 8 wherein the condensation product is isolated by distillation in a high vacuum.

12. A method of making a hydrogenated in-v dane-dione compound comprising reacting methyl-cyclopentene-dione with butadiene.

13. A method of making a hydrogenated indane-dione compound comprising reacting methyl-cyclopentene-dione with a l-vinyl-BA- dihydro-naphthalene.

14. A method of making a hydrogenated in-' dane-dione 7 compound comprising reacting methyl-cyclopentene-dione with a 1-vinyl-3,4- dihydrO-G-R-naphthalene wherein R. is a member of the group consisting of hydroxyl and groups capable of being converted with the aid of hy- 4o drolysis into a hydroxy group.

ELISABETH 

